CN100406426C - Process for production of alicyclic (meth) allyl esters for plastic lens compositions - Google Patents
Process for production of alicyclic (meth) allyl esters for plastic lens compositions Download PDFInfo
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- CN100406426C CN100406426C CNB018110983A CN01811098A CN100406426C CN 100406426 C CN100406426 C CN 100406426C CN B018110983 A CNB018110983 A CN B018110983A CN 01811098 A CN01811098 A CN 01811098A CN 100406426 C CN100406426 C CN 100406426C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
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Abstract
An alicyclic (meth)allyl ester monomer obtained by a transesterification process. An alicyclic (meth)allyl ester compound for plastic lenses which can be obtained by a simple and easy production process and which can endure a long-term storage, is produced using the monomer, and a plastic lens is obtained using the compound.
Description
The cross reference of related application
The application is the application that proposes down at 35U.S.C § 111 (a), according to 35 § 111 (b), requires the right according to 35U.S.C. § 119 (e) (1) of the applying date of the provisional application 60/221,209 that proposed on July 27th, 2000.
Technical field
The present invention relates to the transesterify of alkyl ester with (methyl) allyl ester of the polyprotonic acid by having alicyclic structure, production has the method for (methyl) allyl ester monomer (hereinafter referred is " alicyclic (methyl) allyl ester monomer ") of alicyclic structure at intramolecularly, the method that use is produced alicyclic (methyl) allyl ester compound by alicyclic (methyl) the allyl ester monomer and the polyvalent alcohol of aforesaid method production as starting raw material, and pass through alicyclic (methyl) allyl ester compound that this method is produced.
The invention still further relates to the plastic lens composition that contains above-mentioned alicyclic (methyl) allyl ester compound, by plastic lens that solidifies the said composition acquisition and the method for producing plastic lens.
In addition, the present invention relates to comprise the plastic lens composition of alicyclic (methyl) allyl ester compound, said composition can be used for producing plastic lens, suppresses the generation of uneven dyeing simultaneously and prevents that simultaneously mould is damaged; By solidifying the plastic lens that said composition obtains; With the method for producing plastic lens.
Term used herein " (methyl) vinyl carbinol " is meant vinyl carbinol, methallyl alcohol and/or their mixture.Term used herein " (methyl) allyl ester monomer " is meant allyl ester monomer, methyl allyl ester monomer and/or their mixture.Term used herein " (methyl) allyl ester compound " is meant allyl ester compound, methyl allyl ester compound and/or their mixture.
Background technology
Alicyclic (methyl) allyl ester monomer that alkyl ester by making the polyprotonic acid with alicyclic structure and vinyl carbinol or methallyl alcohol reaction obtain is the hyperergy monomer.This monomer uses with various linking agents or reactive diluent, and the polymkeric substance of this monomer itself is widely used in various moulded partss, laminate, decoration sheet etc., because it has excellent electric performance, dimensional stability, thermotolerance, weatherability, chemical-resistant and mechanical property.In recent years, find that also this polymkeric substance has excellent optical property, and they have begun to use as optical material.
Compare with acrylic resin, the polymerization rate of two (allyl carbonate) resins of the polyoxyethylene glycol of Shi Yonging is low so far, and therefore, their polyreaction is controlled easily.As a result, can obtain uniform polyreaction, and advantageously, the optical strain of the plastic lens that is obtained by two (allyl carbonate) resins of polyoxyethylene glycol is little.
For by polyoxyethylene glycol two (allyl carbonates) but the dyeability of the plastic lens that resin obtains, the plastic lens that is obtained by casting is by at high temperature in dye bath under the painted situation of the usual manner of immersion lens therein, compare with the plastic lens that is obtained by other resin, stain density is known to be excellent.
Yet the problem that two (allyl carbonate) resins of polyoxyethylene glycol exist is when the plastic lens that is obtained by this resin is colored, and has produced uneven dyeing.
In order to overcome this problem, international monopoly publication Nos.WO99/17137 and WO99/38899 disclose the purposes of the allyl ester compound that contains the polycarboxylate structure with alicyclic structure.In these publications, but claim and to obtain the required level dyeing of plastic lens dyeability, promptly providing improvement effect aspect the uneven dyeing reducing.
Yet, depending on production method as the allyl ester of starting raw material, above-mentioned allyl ester compound can not satisfy sometimes with lens the requirement of extended storage stability of composition of the optical material that is representative.
The known embodiment of this class allyl ester monomer or the monomeric production method of methyl allyl ester comprises:
1) by carboxyl acyl chloride and the initial synthetic method of alcohol;
2) by an alkali metal salt and the initial synthetic method of alkyl halide of carboxylic acid; With
3) by carboxylic acid and the initial synthetic method of alcohol.
Yet the problem that the application of these methods in producing relevant compound of the present invention exists is, in method 1) in, be expensive as the acyl chlorides of starting raw material.
In employing method 2) situation under, the side reaction that alkyl halide is hydrolyzed to (methyl) vinyl carbinol takes place with quite high ratio, and disadvantageously, separates or reclaim the complicated operation and the cost height of starting raw material and by product.
In method 3) in, generally use strong acid catalyst, but (methyl) vinyl carbinol is to normally used acid catalyst instability, the problem of existence is that two (methyl) allyl ethers produces as by product.Except the yield of (methyl) vinyl carbinol is low, also find, when sulfuric acid or tosic acid use as catalyzer, corresponding allyl ester produces as the by product of catalyzer, these allyl sulphonic acid esters are difficult to separate from target alicyclic (methyl) allyl ester monomer, and then product stability in the standing storage process is lower, can not deal with wherein requiring product to have the purposes of extended storage stability, as be used for the composition of optical material purposes.
In this manual, term " two (methyl) allyl ethers " is meant diallyl ether, dimethyl-allyl ether and/or their mixture.
Of the present invention open
By considering these problems in the ordinary skill, the purpose of this invention is to provide and produce alicyclic (methyl) allyl ester monomer methods, comprise that the alkyl ester (before this as the monomeric starting raw material of alicyclic (methyl) allyl ester) that makes the polyprotonic acid with alicyclic structure reacts in the presence of transesterification catalyst with (methyl) vinyl carbinol, use the production of alicyclic (methyl) allyl ester monomer to have the method for alicyclic (methyl) allyl ester compound of (methyl) allyl ester group in the end, and alicyclic (methyl) allyl ester compound.
Another object of the present invention provides the plastic lens composition that comprises alicyclic (methyl) allyl ester compound, said composition is suitable for producing optical material, especially plastic lens, by solidifying the plastic lens that this plastic lens composition obtains, and the method for producing this plastic lens.
Result as a large amount of investigations of carrying out in order to address the above problem, the inventor has been found that, when when distilling out rudimentary aliphatic alcohol, have the lower aliphatic alkyl ester of polyprotonic acid of alicyclic structure and (methyl) vinyl carbinol when reacting, can produce target alicyclic (methyl) allyl ester monomer by transesterify.In addition, have been found that, use alicyclic (methyl) allyl ester monomer, transesterification reaction by it and polyvalent alcohol, can produce alicyclic (methyl) allyl ester compound that the molecule end has (methyl) allyl ester group, and find that also this alicyclic (methyl) allyl ester compound can be suitable for optical applications.Based on these discoveries, finished the present invention.
More particularly, the present invention (I) produces alicyclic (methyl) allyl ester monomer methods, comprises that the alkyl ester that makes the polyprotonic acid with alicyclic structure and vinyl carbinol and/or methallyl alcohol react in the presence of transesterification catalyst.
The present invention (II) is the method for producing alicyclic (methyl) allyl ester compound of the repeating unit of end construction with formula (1) and formula (2), and the existence that is included in catalyzer will be carried out transesterify by alicyclic (methyl) the allyl ester monomer and the polyvalent alcohol of the present invention (I) production down.The present invention (II) comprises alicyclic (methyl) allyl ester compound of the repeating unit of the have formula end construction of (1) and formula (2), and it is produced by this production method.
Each R wherein
1Independent expression allyl group or methacrylic, each X independently represents by the organic residue of polyvalent carboxylic acid's deutero-with alicyclic structure, and each Y independently represents by having 2-20 carbon atom and the organic residue that contains the polyol derivative of 2-6 hydroxyl, prerequisite is, by ester linkage, the branched structure that X can contain the repeating unit of end group with formula (1) and formula (2) maybe can have R
1, and by ester linkage, Y can contain the branched structure of the repeating unit of end group with formula (1) and formula (2).
The present invention (III) is the plastic lens composition that comprises alicyclic (methyl) allyl ester compound of the present invention (II).
The present invention (IV) is the plastic lens composition that comprises at least a radical polymerization initiator, and the amount of this initiator is all curable components that contain in plastic lens composition of 0.1-10 mass parts/100 mass parts.
The present invention (V) is by solidifying the Plastic Resin that the present invention (III) or plastic lens composition (IV) obtain.
The present invention (VI) is the method for production the present invention's (V) plastic lens.
The accompanying drawing summary
Each 400MHz of described alicyclic allyl ester compound in an embodiment naturally of the following drawings
1The H-NMR spectrogram.
Fig. 1 is the 400MHz of the alicyclic allyl ester compound of acquisition in embodiment 29
1The H-NMR spectrogram.
Fig. 2 is the 400MHz of the alicyclic allyl ester compound of acquisition in comparative example 1
1The H-NMR spectrogram.
Implement best mode of the present invention
Below describe the present invention in detail.
Below described and belonged to the present invention (I) who produces alicyclic (methyl) allyl ester monomer methods.
The polybasic ester with alicyclic structure that uses in the present invention (I) preferably can have dicarboxylic ester, tricarboxylic ester or the tetracarboxylic ester of some other substituent 5-, 6-or 7-unit naphthenic hydrocarbon.Their example comprises 1, the diester of 4-cyclohexane dicarboxylic acid, 1, the diester of 3-cyclohexane dicarboxylic acid, 1,2, tricarboxylic three esters of 4-hexanaphthene, 1,2,4, four esters of 5-hexanaphthene tetracarboxylic acid, the hexanaphthene-1 that alkyl replaces, the diester of 4-dicarboxylic acid, with the hexanaphthene-1 that halogen replaces, the diester of 4-dicarboxylic acid.
Term used herein " alkyl " is meant the alkyl with 1-10 carbon atom, and it can have side chain, and their specific examples comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and the tertiary butyl.The specific examples of " halogen " comprises chlorine, bromine and iodine.
In the middle of these, consider reactive behavior, preferably 1, the diester of 4-cyclohexane dicarboxylic acid, 1, the diester of 3-cyclohexane dicarboxylic acid, the hexanaphthene-1 that the 5-alkyl replaces, the hexanaphthene-1 that the diester of 4-dicarboxylic acid and 5-halogen replace, the diester of 4-dicarboxylic acid, more preferably 1, the diester of 4-cyclohexane dicarboxylic acid and 1, the diester of 3-cyclohexane dicarboxylic acid.
Ester component in the polybasic ester with alicyclic structure that uses in the present invention (I) is not special restriction, as long as it has the group that can carry out transesterify.Their specific examples comprises methyl, ethyl, sec.-propyl, n-propyl, isobutyl-, sec-butyl, the tertiary butyl and normal-butyl.In the middle of these, because preferably have the boiling point of the boiling point that is lower than (methyl) vinyl carbinol, so methyl, ethyl and sec.-propyl are preferred by the alcohol that produces with the transesterify of (methyl) vinyl carbinol.
As mentioned above, term used herein " alicyclic (methyl) allyl ester monomer " is meant such monomer, have alicyclic structure at its intramolecularly, the carboxylic acid group who wherein directly is bonded in alicyclic structure simultaneously has based on the ester structure by (methyl) vinyl carbinol deutero-structure.
Their specific examples comprises 1,4-cyclohexane dicarboxylic acid diallyl, 1,4-cyclohexane dicarboxylic acid dimethyl allyl ester, 1,4-cyclohexane dicarboxylic acid allyl methyl allyl ester, 1,3-cyclohexane dicarboxylic acid diallyl, 1,3-cyclohexane dicarboxylic acid dimethyl allyl ester, 1,3-cyclohexane dicarboxylic acid allyl methyl allyl ester, 1,2,4-hexanaphthene tricarboxylic acid triallyl, 1,2,4-hexanaphthene tricarboxylic acid three (methyl allyl ester), 1,2,4-hexanaphthene tricarboxylic acid diallyl methyl allyl ester, 1,2,4,5-hexanaphthene tetracarboxylic acid tetraene propyl ester, 1,2,4,5-hexanaphthene tetracarboxylic acid triallyl methyl allyl ester, 1,2,4,5-hexanaphthene tetracarboxylic acid diallyl dimethyl allyl ester, 1,2,4,5-hexanaphthene tetracarboxylic acid allyl group trimethylammonium allyl ester, 1,2,4,5-hexanaphthene tetracarboxylic acid tetramethyl-allyl ester, the hexanaphthene-1 of 5-alkyl-replacement, 4-dicarboxylic acid diallyl, the hexanaphthene-1 of 5-alkyl-replacement, 4-dicarboxylic acid allyl methyl allyl ester, the hexanaphthene-1 of 5-alkyl-replacement, 4-dicarboxylic acid dimethyl allyl ester, the hexanaphthene-1 of 5-halogen-replacement, 4-dicarboxylic acid diallyl, the hexanaphthene-1 of 5-halogen-replacement, the hexanaphthene-1 of 4-dicarboxylic acid allyl methyl allyl ester and 5-halogen-replacement, 4-dicarboxylic acid dimethyl allyl ester.
The transesterification catalyst that uses in the present invention (I) fundamentally can be any catalyzer, as long as it can activate ester group and cause and the alcohol reaction.Their example comprises:
Alkali metal, and their oxide compound, salt of weak acid, alkoxide and oxyhydroxide;
Alkali earth metal, and their oxide compound, salt of weak acid, alkoxide and oxyhydroxide;
Hf, Mn, U, Zn, Cd, Zr, Pb, Ti, Co and Sn element and their oxide compound, oxyhydroxide, inorganic acid salt, alkoxide, organic acid salt and organometallic complex;
Organometallic compound includes basic tin compound, as dibutyltin oxide, di-n-octyltin oxide and dichloride dibutyl tin, with organic titanic compound, and as tetralkyl titanate, for example metatitanic acid tetramethyl ester, metatitanic acid tetra isopropyl ester and butyl titanate; With
Tertiary amine, as xylidine and 1,4-diazabicyclo [2.2.2] octane.
In the middle of these, preferably:
An alkali metal salt of organic acid and/or mineral acid and the oxyhydroxide of alkaline-earth metal and/or hopcalite;
Organo-tin compound such as dibutyltin oxide, di-n-octyltin oxide and dichloride dibutyl tin;
Tetralkyl titanate such as metatitanic acid tetramethyl ester, titanium isopropylate and butyl titanate;
An alkali metal salt of carbonic acid and alkaline earth salt are as salt of wormwood and lime carbonate;
Alkali-metal alkyl alkoxide, as potassium methylate, sodium methylate, potassium ethylate, and potassium tert.-butoxide;
Tertiary amine such as xylidine and 1,4-diazabicyclo [2.2.2] octane; With
The organometallic complex of hafnium is as Acetyl Acetone acid hafnium.These can use with their form of two or more mixtures.
Especially, consider industrial production, the an alkali metal salt of organic acid and/or mineral acid and the oxyhydroxide of alkaline-earth metal and/or hopcalite are preferred, because catalyst component precipitates after reaction is finished, product only can separate by filtering with catalyzer.
Comprise calcium hydroxide, magnesium hydroxide, hydrated barta, calcium oxide and magnesium oxide as the oxyhydroxide of the alkaline-earth metal of catalyzer and the specific examples of oxide compound.Wherein, according to ability, calcium hydroxide and calcium oxide are preferred.
The specific examples of mineral acid of Cun Zaiing or organic acid an alkali metal salt comprises sodium acetate together, potassium acetate, lithium acetate, rubidium acetate, cesium acetate, Repone K, sodium-chlor, sodium sulfate, vitriolate of tartar, salt of wormwood, yellow soda ash, Quilonum Retard, rubidium carbonate, potassiumphosphate, saltpetre, sodium bicarbonate and cesium carbonate.In the middle of these, in view of their ability, potassium acetate, sodium acetate, rubidium acetate and cesium acetate are preferred.
In the oxyhydroxide and/or hopcalite of an alkali metal salt of organic acid and/or mineral acid and alkaline-earth metal, the mixture of calcium hydroxide and cesium acetate preferably, the mixture of calcium oxide and cesium acetate, the mixture of calcium hydroxide and rubidium acetate, the mixture of calcium hydroxide and potassium acetate, the mixture of calcium oxide and potassium acetate, the mixture of the mixture of calcium hydroxide and sodium acetate and calcium oxide and sodium acetate, and the mixture of calcium hydroxide and cesium acetate more preferably, the mixture of calcium hydroxide and potassium acetate, the mixture of the mixture of calcium hydroxide and rubidium acetate and calcium oxide and potassium acetate.
For usage rate, the consumption of an alkali metal salt of organic acid and/or mineral acid is 0.001-1 mass parts, the more preferably oxyhydroxide and/or the oxide compound of the alkaline-earth metal of 0.01-0.5 mass parts/1 mass parts preferably.
If the ratio of an alkali metal salt of organic acid and/or mineral acid and the oxyhydroxide of alkaline-earth metal and/or oxide compound is lower than this scope, reaction cost unfriendly is long-time, and if it surpasses this scope, reaction soln may be seriously painted, this is not preferred.
Employed reaction formation is the method that heating has polyprotonic acid with the multivalence ester of (methyl) vinyl carbinol of alicyclic structure in the presence of catalyzer.Reaction is preferably at 30-200 ℃, and more preferably 50-150 ℃ temperature at normal atmosphere or impressed pressure, or if desired, is under reduced pressure carried out in atmosphere of inert gases.In order more effectively to react, preferably distill the alcohols that produces by response procedures at once.
(methyl) vinyl carbinol must be at least uses with the theoretical amount of starting raw material ester, and when considering speed of response, balance etc., (methyl) vinyl carbinol preferably uses with the molar excess number.Yet, if (methyl) vinyl carbinol too much uses, do not demonstrate this excessive effect of contending with, consider that from the benefit aspect this is not preferred.Therefore, (methyl) vinyl carbinol is with 1.2-10 times (mol), and the more preferably doubly amount use of (mol) of 1.5-4 is based on the theoretical amount of starting raw material ester.Starting raw material ester and (methyl) vinyl carbinol can reaction begin add or can during reaction add according to the order of sequence.
Catalyst consumption is 0.01-2 quality %, and preferably approximately 0.1-1 quality % is if consumption very little, then speed of reaction descends, if and consumption surpasses above-mentioned scope, not only can not obtain to compensate the effect of this amount, and some decline owing to side reaction of serious painted or yield has taken place.In addition, excessive use has caused the problem with considerable time of catalyst separating needs and work.
The notable feature that is separated in alicyclic (methyl) allyl ester monomer methods that produces in the reactive system of the present invention is, when using above-mentioned mixed catalyst, by after distilling out (methyl) vinyl carbinol, using suitable mode such as filtering separation catalyzer, then residue is carried out acid elution and neutralizing treatment, can obtain the purified product that uses as product.
Even under the situation of using other catalyzer,, can obtain the high quality product by using suitable way such as distillation purifying reaction product.
The present invention (II) is below described.The present invention (II) is the method for producing alicyclic (methyl) allyl ester compound of the repeating unit of end construction with formula (1) and formula (2), and the existence that is included in catalyzer will be carried out transesterify by alicyclic (methyl) allyl ester monomer and the polyvalent alcohol that the present invention (I) produces down.The present invention (II) comprises alicyclic (methyl) allyl ester compound of the repeating unit of the have formula end construction of (1) and formula (2), and it is produced by this production method.
Each R wherein
1Independent expression allyl group or methacrylic, each X independently represents by the organic residue of polyvalent carboxylic acid's deutero-with alicyclic structure, and each Y independently represents by having 2-20 carbon atom and the organic residue that contains the polyol derivative of 2-6 hydroxyl, prerequisite is, by ester linkage, X can contain end group with formula (1) and formula (2) repeating unit branched structure or can have R
1, and by ester linkage, Y can contain the branched structure of the repeating unit of end group with formula (1) and formula (2).
The alicyclic allyl ester compound that is used for the repeating unit of end construction with formula (1) of the present invention and formula (2) can carry out transesterify by (methyl) allyl ester that will be produced by the present invention (I) and polyvalent alcohol and produce in the presence of catalyzer.
The catalyzer of the production stage of the alicyclic allyl ester compound of the repeating unit of be used to the to have formula end construction of (1) and formula (2) is not special restriction, as long as it is the catalyzer that can generally be used for transesterify.Organometallic compound is preferred, and their object lesson comprises tetraisopropoxy titanium, four titanium n-butoxide, and dibutyltin oxide, di-n-octyltin oxide, Acetyl Acetone acid hafnium and zirconium acetylacetonate, yet, the invention is not restricted to these.In the middle of these, dibutyltin oxide and di-n-octyltin oxide are preferred.
Temperature of reaction in this production stage is not special restriction, yet, preferably 100-230 ℃ of temperature of reaction, more preferably 120-200 ℃.Under the situation of using solvent, temperature of reaction is limited by the boiling point of solvent sometimes.
In this production stage, do not use solvent usually, yet, if desired, can use solvent.The solvent that can use is not special restriction, as long as it does not suppress transesterify.Their object lesson comprises benzene, toluene, and dimethylbenzene and hexanaphthene, but the invention is not restricted to these.In the middle of these, benzene and toluene are preferred.Yet as mentioned above, this production stage can also carry out without solvent.
The alicyclic allyl ester compound of the repeating unit of end construction with formula (1) by aforementioned production method production or formula (2) is below described.
In formula (1), each R
1Independent expression allyl group or methacrylic.In formula (1) or (2), each X independently represents by the organic residue of polyvalent carboxylic acid's deutero-with alicyclic structure.
Term used herein " each R
1Independent expression allyl group or methacrylic " be meant that the end group of being represented by formula (1) all can be an allyl group, all can be methacrylic, part can be that allyl group or part can be methacrylics.
Term used herein " each X independently represents " is meant that in following structural formula (3), as an example of the repeating unit of being represented by formula (1) or (2), each X that contains is independent of each other in repeating structure.
This describes by reference example such as structural formula (3) following, and it has shown that Y wherein is the situation by the organic residue of ethylene glycol deutero-:
Wherein each X independently represents to represent integer more than 0 or 1 or 1 by organic residue of polyvalent carboxylic acid's deutero-with alicyclic structure and q.
In structural formula (3), (q+1) X of number can be all by the organic residue of polyvalent carboxylic acid's deutero-with different alicyclic structures (promptly, organic residue is derived one by one by the polyvalent carboxylic acid with (q+1) kind alicyclic structure), perhaps can be all by the organic residue of polyvalent carboxylic acid's deutero-with identical alicyclic structure (that is, (q+1) organic residue of number is derived by the polyvalent carboxylic acid with a kind of alicyclic structure).Can also form mixed structure, wherein in the middle of organic residue of (q+1) number, some organic residues are derived by the polyvalent carboxylic acid with identical alicyclic structure and some other is derived by the polyvalent carboxylic acid with dissimilar alicyclic structures.In addition, mixed structure can be random in entire structure fully, and perhaps in mixed structure, part can repeat.
When part or all of X has three or three above carboxyls and when having the organic residue of polyvalent carboxylic acid's deutero-of alicyclic structure, partly or entirely X maybe can have R by the branched structure that ester bond can contain the repeating unit of end group with formula (1) and formula (2)
1More particularly, being used as serves as reasons has an example of organic residue of the trivalent of alicyclic structure or the above carboxylic acid derivatives of trivalent, when organic residue is present among the X, can have part-structure by following structural formula (4) expression as the present invention's (II) of the repeating unit of end construction with formula (1) and formula (2) alicyclic allyl ester compound:
Wherein each Y independently represents by having 2-20 carbon atom and the organic residue that contains the polyol derivative of 2-6 hydroxyl.
Certainly, though when part or all of X be by having 3 or 3 above carboxyls and when having the organic residue of polyvalent carboxylic acid's deutero-of alicyclic structure, each X can not have branched structure fully.
Carboxyl can former state keep.Especially, therein part or all X be when having 3 or 3 above carboxyls and not having the organic residue of polyvalent carboxylic acid's deutero-of branched structure, do not have the carboxyl in the structure division of branched structure former state to keep, and alicyclic (methyl) allyl ester compound of the present invention (II) can also comprise this compound.
In formula (1) or (2), each X independently represents by the organic residue of polyvalent carboxylic acid's deutero-with alicyclic structure.
The specific examples of " polyvalent carboxylic acid with alicyclic structure " used herein comprises 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 4-methyl-cyclohexyl alkane-1,2-dicarboxylic acid, 3-methyl-cyclohexyl alkane-1,2-dicarboxylic acid and 1,2,4-hexanaphthene tricarboxylic acid.Much less, the invention is not restricted to these, and these acid can be separately or use with their two or more mixture.
Have among the polyvalent carboxylic acid of alicyclic structure at these, with regard to the flowability and transesterify performance of the alicyclic allyl ester compound of the repeating unit of end construction with formula (1) and formula (2), preferably 1, the 2-cyclohexane dicarboxylic acid, 1, the 3-cyclohexane dicarboxylic acid, 1, the 4-cyclohexane dicarboxylic acid, 4-methyl-cyclohexyl alkane-1, the 2-dicarboxylic acid, 3-methyl-cyclohexyl alkane-1, the mixture of two or more of 2-dicarboxylic acid and they, more preferably 1, the 3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid and their mixture.
In formula (2), each Y independently represents by having 2-20 carbon atom and the organic residue that contains the polyol derivative of 2-6 hydroxyl.
Term used herein " each Y independently represents " is meant in following formula (5), as by formula
(2) Biao Shi repeating unit example, the Y of the number m that contains in repeating structure is independently each other.
This describes in following reference example such as following structural formula (5), and it has shown wherein X by 1,4-cyclohexane dicarboxylic acid deutero-situation.
Wherein each Y independently represents by having 2-20 carbon atom and contain organic residue of the polyol derivative of 2-6 hydroxyl, and m represents the integer more than 0 or 1 or 1.
In structural formula (5), the Y of number m can all be by organic residue of different polyol derivatives (promptly, organic residue is derived one by one by m kind polyvalent alcohol), perhaps all can be organic residue (that is, organic residue of number m is by a kind of polyol derivative) by identical polyol derivative.Can also form mixed structure, wherein in the middle of the Y of number m, some are to be organic residue by dissimilar polyol derivatives by organic residue of the polyol derivative of same type and some other.In addition, mixed structure can be fully random in entire structure, and perhaps in mixed structure, part can repeat.
Therein part or all Y be under the situation by organic residue of polyol derivative with 3 or 3 above hydroxyls, by ester linkage, partly or entirely Y can further contain the branched structure of the repeating unit of the have formula end group of (1) and formula (2).More particularly, for example, when being present among the Y by the organic residue of TriMethylolPropane(TMP) deutero-as an example of trivalent alcohol, the alicyclic allyl ester compound of the present invention's (I) the end construction with formula (1) and the repeating unit of formula (2) can have the part-structure with following structural formula (6) expression:
Wherein each X independently represents by the organic residue of polycarboxylic acid deutero-with alicyclic structure.
Certainly, even when part or all of Y is organic residue by the polyol derivative with 3 or 3 above hydroxyls, Y can not have branched structure fully.
Hydroxyl can former state keep.Especially, therein part or all Y be by having 3 or 3 above hydroxyls and not having under the situation of organic residue of polyol derivative of branched structure, hydroxyl in not having the structure division of branched structure can former state keep, and alicyclic (methyl) allyl ester compound of the present invention (II) can also comprise this compound.
In formula (2), each Y independently represents by having 2-20 carbon atom and one or more organic residues that contain the polyol derivative of 2-6 hydroxyl.The example of " having 2-20 carbon atom and the polyvalent alcohol that contains 2-6 hydroxyl " used herein comprises following compound.
The specific examples of dibasic alcohol comprises ethylene glycol, propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,3 butylene glycol, neopentyl glycol, hexamethylene glycol and 1,4 cyclohexane dimethanol.
Ternary or more the specific examples of higher polyol comprise glycerine, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, Dipentaerythritol and sorbyl alcohol.In addition, can use the dibasic alcohol that in main chain, contains ether, as glycol ether, dipropylene glycol, triglycol and polyoxyethylene glycol.Can also use two or more mixture of these polyvalent alcohols.Much less, the invention is not restricted to these concrete examples.
In these polynary saturated alcohol, with regard to the flowability of the alicyclic allyl ester compound of the repeating unit of end construction with formula (1) and formula (2), propylene glycol preferably, neopentyl glycol, 1,4-butyleneglycol and glycol ether, propylene glycol and 1 more preferably, the 4-butyleneglycol.
With the repetition number of the group of formula (2) expression is not special restriction.Can also use the mixture of material with various repetition number.In addition, repetition number is that 0 material can be that the material of the integer more than 1 or 1 is used in combination with repetition number wherein.Yet from realizing the viewpoint of the object of the invention, only using repetition number wherein is that 0 compound is not preferred.
Usually, as the repeating unit of the present invention's (II) alicyclic allyl ester compound by the repetition number of the group of formula (2) the expression integer of 1-50 preferably.Be used for plastic lens composition if only comprise the alicyclic allyl ester compound that repetition number surpasses 50 compound, allyl group concentration reduces so, this can cause disadvantageous effect, for example, when solidifying, curing can be prevented from, and perhaps part of compounds can keep uncured, thereby has reduced the physicals such as the mechanical property of cured product.In the whole compounds that contain in alicyclic allyl ester compound, repetition number is 1-50 preferably, more preferably 1-30, the also more preferably integer of 1-10.
Depend on working condition, be retained in as alicyclic (methyl) allyl ester monomer of starting raw material in the alicyclic allyl ester compound of repeating unit of the have formula end construction of (1) and formula (2), and this monomer can former state use in plastic lens material.Yet, if alicyclic (methyl) allyl ester monomer as starting raw material exists with 70 quality % or more than the 70 quality %, total amount based on the present invention's (II) alicyclic allyl ester compound, when the compound blend of this compound and formula (3) when preparing plastic lens composition described below, can produce dyeing speck unfriendly, perhaps when separating cured product from glass mold, mould may be damaged.
The present invention (III) and the present invention's (IV) plastic lens composition is below described.The present invention (III) is the plastic lens composition that comprises alicyclic (methyl) allyl ester compound of the present invention (II).
The present invention (IV) is the plastic lens composition that comprises at least a radical polymerization initiator, and the consumption of this initiator is all curable components that contain in plastic lens composition of 0.1-10 mass parts/100 mass parts.
The compound of usefulness formula (7) expression that can contain in the present invention (III) or the present invention's (IV) plastic lens composition can synthesize by usual way.Their example is included in the method that makes carbonic acid two (methyl) allyl ester and polyvalent alcohol carry out transesterify under the existence of catalyzer and (consults, Japan unexamined patent publication No.3-66327, JP-B-3-66327) and the method for (methyl) vinyl carbinol and phosgene and polyol reaction (is consulted, U.S. patent Nos.2,370,565 and 2,592,058), but the invention is not restricted to these.
Term used herein " carbonic acid two (methyl) allyl ester " is meant at least a compound that is selected from carbonic acid diallyl, carbonic acid dimethyl allyl ester, carbonic acid allyl methyl allyl ester and their mixture.
Wherein Z represents that n represents the integer of 2-6, R by having 2-20 carbon atom and the one or more organic residues of polynary saturated alcohol deutero-that contain the hydroxyl of number n
2Expression allyl group or methacrylic, prerequisite is each R
2Be independently, s represents 0 integer to (n-1), and t is 1 to n integer, and s+t=n.
In formula (3), Z represents by having 2-20 carbon atom and the one or more organic residues of polynary saturated alcohol deutero-that contain 2-6 hydroxyl.The example of " having 2-20 carbon atom and the polynary saturated alcohol that contains 2-6 hydroxyl " used herein comprises following compound.
The specific examples of binary saturated alcohol comprises ethylene glycol, propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,3 butylene glycol, neopentyl glycol, hexamethylene glycol and 1,4 cyclohexane dimethanol.
The specific examples of ternary or more senior polynary saturated alcohol comprises glycerine, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, Dipentaerythritol and sorbyl alcohol.In addition, can also use the binary saturated alcohol that in main chain, contains ether, as glycol ether, dipropylene glycol, triglycol or polyoxyethylene glycol.Can also use two or more mixture of these alcohol.Much less, the invention is not restricted to these concrete examples.
In these polynary saturated alcohol, ethylene glycol preferably, propylene glycol, glycol ether and dipropylene glycol, more preferably glycol ether.When using glycol ether as polynary saturated alcohol, gained poly-(allyl carbonate) is glycol ether two (allyl carbonate), and their specific examples comprises CR-39 (trade(brand)name is produced by PPG), with Nouryset 20 (trade(brand)name is produced by Akzo Nobel).
In formula (7), R
2Expression allyl group or methacrylic, prerequisite is each R
2Be independently.For example, when n was 3, the compound of formula (7) was the mixture with the compound of following structural formula (8)-(10) expression:
In these compounds, for example in structural formula (8), three R
2Can all be allyl group or can all be methacrylic.Also feasible is two R
2Be allyl group and a R
2Be methacrylic, or a R
2Be allyl group and two R
2It is methacrylic.Certainly, same situation is adapted to two R in the structural formula (9)
2And the R in the structural formula (10)
2
In formula (7), Z is by having 2-20 carbon atom and the one or more organic residues of polynary saturated alcohol deutero-that contain 2-6 hydroxyl.Have when producing as the compound of Z for the organic residue of polynary saturated alcohol deutero-that surpasses 6 integer if plastic lens composition uses, can reduce unfriendly by the impact-resistance that solidifies the plastic lens that said composition obtains by hydroxyl value wherein.Also have, if using, the Plastic Resin composition has by hydroxyl value wherein for less than the organic residue of saturated alcohol deutero-of 2 integer (promptly 1) during as the compound production of Z, extremely reduce by the thermotolerance and the solvent resistance of solidifying the plastic lens that obtains, this is not preferred.
Suppose that the hydroxyl value among the Z is n, s be 0 and n-1 between any integer, t be 1 and n between any integer, and s+t is n.In formula (7), if t is the integer more than at least 1 or 1, it is exactly enough, but in view of the physicals of final plastic lens, preferred hydroxyl as much as possible is replaced by carbonate group.Though can change less than the composition ratio of each compound of n according to t wherein, wherein t is that the compound of n preferably accounts for 80 quality % or more than the 80 quality % in the compound by formula (7) expression, more preferably 90 quality % or more than the 90 quality %.
The blending amount of the present invention's (II) alicyclic allyl ester compound is 0.1-20 quality % preferably, more preferably 1-15 quality %, more preferably 2-10 quality % also is based on all curable components that contain in the present invention (III) or the present invention's (IV) plastic lens composition.If the blending amount of compound is lower than 0.1 quality %, may can not show the effect that reduces uneven dyeing, and if blending amount surpasses 20 quality %, reduced rate of profit unfriendly.
Term used herein " component that all are curable " be meant by the compound of formula (1) expression, by the compound of formula (2) expression and with by the compound of formula (1) expression or by the copolymerizable monomeric total amount of compound of formula (2) expression.
Amount with the compound of formula (3) expression is 60-99.9 quality %, preferred 75-99 quality %, more preferably 80-98 quality %.If this blending amount is less than 60 quality %, can be by the plastic lens that curing composition obtains in mechanical property and optical property upper variation, and if it is above 99.9 quality %, with disadvantageous appearance dyeing failure.
The present invention (III) or the present invention's (IV) plastic lens composition can contain with the gathering of formula (7) expression (allyl carbonate) or with the end construction with formula (1) and formula (2) but one or more monomers of copolymerization of alicyclic allyl ester compound of repeating unit, main purpose is the viscosity of regulating composition, its amount is in the scope that is no more than 20 quality %, based on all curable components that contain in plastic lens composition of the present invention.
Monomeric example comprise have acryl, vinyl or allylic monomer.Monomeric specific examples with acryl comprises (methyl) methyl acrylate and (methyl) isobornyl acrylate; Monomeric specific examples with vinyl comprises vinyl-acetic ester and vinyl benzoate; And have allylic monomeric specific examples and comprise 1,2-cyclohexane dicarboxylic acid diallyl, 1,3-cyclohexane dicarboxylic acid diallyl and 1,4-cyclohexane dicarboxylic acid diallyl.Certainly, the invention is not restricted to these specific exampless, in the scope of the physicals of not damaging the plastic lens that obtains by curing, can also use Phthalic acid, diallyl ester, diallyl p phthalate, diallyl isophthalate, phenylformic acid allyl ester etc.
Consider the processing characteristics in the casting, the viscosity of the present invention (III) or the present invention's (IV) plastic lens composition generally is at 10-10 under 25 ℃, 000mPa.s, and preferred 10-5,000mPa.s is more preferably in the scope of 10-500mPa.s.
Term used herein " viscosity " is meant the viscosity with rotary viscosity design determining.Rotational viscosimeter is described in detail in Iwanami Rikagaku Jiten (Iwanami Physics and ChemistryEncyclopedia), 3
RdEd.8
ThImp. in (on June 1st, 1977).
Monomeric addition is 20 quality % or below the 20 quality %, preferred 10 quality % or below the 10 quality % and more preferably 5 quality % or below the 5 quality %, based on all curable components that contain in plastic lens composition of the present invention.If monomer adds to surpass 20 quality %, can reduce required physicals such as the optical property of plastic lens that obtains by curing composition.By poly-(allyl carbonate) and the kind of allyl ester oligomers and desired physical properties value such as the optical property of considering in plastic lens composition, to contain that mixing when passes through to solidify the plastic lens that obtains, select best monomer.
The present invention's (IV) plastic lens composition can contain the radical polymerization initiator as solidifying agent, and this is preferred.
Can be added to radical polymerization initiator in the plastic lens composition of the present invention (IV) and not be special restriction, can add known radical polymerization initiator, as long as it does not have physicals value such as the optical property of disadvantageous effect by the plastic lens of curing composition acquisition.
Yet being used for radical polymerization initiator of the present invention preferably dissolves in other component that is present in the cured compositions of wanting and preferably produces down free radical at 30-120 ℃.The specific examples of the radical polymerization initiator that can add comprises di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, the peroxy dicarbonate di-n-propyl ester, peroxide-butyl carbonate and t-butylperoxyl benzoate, but the invention is not restricted to these.In view of curing performance, di-isopropyl peroxydicarbonate is preferred.
The addition of radical polymerization initiator is in the 0.1-10 mass parts, in the scope of preferred 1-5 mass parts, based on all curable components that contain in plastic lens composition of the present invention.If this addition is less than 0.1 mass parts, composition can solidify insufficient, and if it surpasses 10 mass parts, reduced rate of profit unfriendly.
The present invention (III) or the present invention's (IV) plastic lens composition can contain that normally used additive as tinting material, comprises dyestuff and pigment for the performance of improving plastic lens, UV light absorber, releasing agent and antioxidant.
The example of tinting material comprises pigment dyestuff such as anthraquinone class, azo class, carbon
Class, quinoline, quinone imides, indigoid and phthalocyanines; Organic dye such as azoic dyestuff and sulphur dyestuff; With mineral dye such as titan yellow, iron oxide yellow, zinc yellow, chrome orange, chrome vermillion, cobalt violet, cobalt blue, cobalt green, chromium sesquioxide, titanium dioxide, zinc sulphide and carbon black.
The example of releasing agent comprises stearic acid, butyl stearate, Zinic stearas, stearylamide, fluorochemicals and silicon compound.
The example of UV light absorber comprises triazole such as 2-(2 '-hydroxyl-tert-butyl-phenyl) benzotriazole, benzophenone such as 2,4 dihydroxyl benzophenone, salicylate such as Whitfield's ointment 4-tertiary butyl phenyl ester and steric hindrance amine such as two-(2,2,6,6-tetramethyl--4-piperidyl) sebate.
The example of antioxidant comprises phenols such as 2,6 di tert butyl 4 methyl phenol and four [methylene radical-3-(3 ', 5 '-di-t-butyl-4-hydroxyphenyl) propionic ester] methane; Sulfocompound is as 3,3 '-Tyox B; With phosphorous antioxidant such as trisnonyl phenyl phosphite.
Additive is the interpolation total amount 1 quality % or below the 1 quality %, based on all curable resin Compositions that contain in plastic lens resin composition of the present invention preferably of tinting material (comprising dyestuff and pigment), UV light absorber, releasing agent and antioxidant for example.
The plastic lens of the present invention (V) is below described.The present invention (V) is the plastic lens that obtains by the plastic lens composition that solidifies the present invention (III) or the present invention (IV).
Plastic lens of the present invention preferably has the refractive index of 1.497-1.505 under 25 ℃.Is the mould that only is suitable for producing the plastics with identical refractive index using the compound by formula (7) expression as the mould that uses in the raw material production plastic lens (refractive index: 1.498,25 ℃).As long as use identical mould, the variation of refractive index means the variation of lens performance.
For the composition by the lens that are used to have high index obtains plastic lens with same capabilities, different moulds is essential.Therefore, the refractive index of removing unrestricted gained lens is so that eliminate the more necessity of mold exchange, otherwise can not obtain to have the alicyclic allyl ester compound of the repeating unit of the end construction of formula (1) and formula (2) owing to introducing, by the compound of formula (7) expression and with the alicyclic allyl ester compound of the repeating unit of end construction with formula (1) and formula (2) or with by formula (7) but the monomeric lens performance of the compound copolymerization of expression improve.The refractive index of plastic lens of the present invention preferably 1.498-1.505, more preferably 1.498-1.503 under 25 ℃.
The present invention (VI) is below described.The present invention (VI) is the production method of the present invention's (V) plastic lens, comprises the plastic lens composition that solidifies the present invention (III) or the present invention (IV).
In the present invention, the Mould Machining of plastic lens composition is fit to be undertaken by casting.Their specific examples comprises radical polymerization initiator is added in the composition, by pipeline mixture injected mould with elastomerics packing ring or spacers, the method that is heating and curing again in baking oven.
The building material of mould used herein is metal or glass.Generally, after casting, must clean the mould of plastic lens, this cleaning uses strong base solution or strong acid to carry out usually.Do not resemble metal, glass is cleaned change hardly, and in addition, glass is easy to polishing, thereby has reduced surfaceness significantly.From these reasons as can be seen, glass is preferred the use.
The present invention (III) or the present invention's (IV) plastic lens composition has alicyclic structure, therefore, therefore, refractive index can approachingly easily originate from the refractive index 1.498 of the plastic lens of the polyoxyethylene glycol two (allyl carbonate) that is used for plastic lens in many cases.This is favourable, because mould or the analogue that is generally used for molding need not change, but can former state use.
Solidification value during molding is about 30-120 ℃, preferred 40-100 ℃, consider contraction or strain when solidifying, and preferably handle solidification value, make and carry out gradually when being solidificated in elevated temperature.Generally be 0.5-100 hour set time, preferred 3-50 hour, and more preferably 10-30 hour.
The method of plastic lens of the present invention of dyeing is not special restriction.Can use any method, as long as it is the known dyeing process that is used for plastic lens.In the middle of these, be preferred as the dip-dye method of general known usual way." dip method " used herein is meant and dispersed dye is dispersed in the water with tensio-active agent so that preparation dye bath and under heating plastic lens being immersed in this dyeing solution, thus the method for coloured plastics lens.
The method of coloured plastics lens is not limited to the dip dyeing method, but can use other currently known methods, as thereby the method for distil pigment dyestuff and coloured plastics lens (is consulted, Japan unexamined patent publication No.35-1384, JP-B-35-1384) thereby and the method for distillation sublimable dyestuff and coloured plastics lens (consult, Japan unexamined patent publication Nos.56-159376 and 1-277814, JP-B-56-159376 and JP-B-1-277814).In view of simple to operate, dip method is most preferred.
Below further specify the present invention by reference embodiment, yet, should not be considered as the present invention and be subject to these embodiment.
Below provided the measuring condition of vapor-phase chromatography of using in an embodiment (hereinafter referred is " GC ") and liquid phase chromatography (hereinafter referred is " LC ").
The GC condition
Employed device: GC-14B (producing) by Shimadzu Corp.
Detector: flame ionization ditector
Measuring method: internal standard method (internal standard material: n-butyl acetate)
Injection temperature: 220 ℃
Temperature condition:
Temperature kept 10 minutes down at 40 ℃, after this raise with 5 ℃/minute speed and kept 10 minutes down at 220 ℃ then.
Used pillar DB-WAX is (by J﹠amp; W produces), internal diameter: 0.25mm, length: 30m
The LC condition
Eluent: 0.1 quality % phosphate aqueous solution: vinyl cyanide=60: 40 (v/v)
Flow velocity: 1ml/min
Detector: RI detector
Measuring method: internal standard method (internal standard material: ethyl acetate)
Used pillar: 2 series connection pillars of Shodex ODSpak F-511
Oven temperature: 40 ℃
The following measurement of various physicalies.
1, refractive index (n
D) and Abb (v
D)
The sample of preparation 9mm * 16mm * 4mm uses " the AbbeRefractometer 1T " that made by Atago at room temperature to measure refractive index (n
D) and Abb (v
D).The solvent contact that uses is α-bromonaphthalene.
2, viscosity
Viscosity uses the Brookfield viscometer of being produced by Tokyo Keiki Co.Ltd. (Model B8U) to measure viscosity.
3, the measuring method of Hazen colour
The Hazen colour is by measuring in the method described in the JIS K-0071-1.
4, Barcol hardness
Barcol hardness uses Model 934-1 to measure according to JIS K-6911.
5, the evaluation of dyeing process and uneven dyeing
In the 1L beaker, add Sumikaron Blue E-FBL (producing) and the water of 0.5L, the dissolving under agitation again of 0.8g by SumitomoChemical Co.Ltd..Gained solution 80 ℃ of down heating, will be fixed in support separately again so that the solidified plastic lens sample that is not laminated to each other is impregnated in this disperse dye solutions under 80 ℃, and keep 10 minutes in water-bath.After this, take out sample, water thoroughly washs, then hot-air dry in 30 ℃ baking oven.
With observing the plastic lens sample of examining such acquisition, dyeing outward appearance and show that with uneven dyeing those are rated as " defectiveness " uniformly not.In evaluation, use 30 solidified sample altogether, calculate the number of " defectiveness " sample.
Embodiment 1
Add 1 of 100g to 300ml three-necked flask with thermometer and rectifying tower, 4-cyclohexane dicarboxylic acid dimethyl ester (hereinafter referred is " CHDM "), the vinyl carbinol of 120g, the calcium hydroxide of 0.25g and 0.05g potassium acetate, and reaction under the oil bath that transfers to 120 ℃ is heated.Reaction was carried out 10 hours, distilled out with reaction from rectifying tower simultaneously and carried out and the methyl alcohol that produces.After reaction is finished, analyze to confirm by GC, obtained 98.8% 1,4-cyclohexane dicarboxylic acid diallyl is based on CHDM.After this, under reduced pressure distill out the vinyl carbinol in the system of being retained in, again by removing by filter catalyzer.Filtrate is almost colourless transparent liquid, and its Hazen colour is 5.
This filtrate of straight run distillation under reduced pressure obtains the water white transparency 1 of the boiling point with 140-142 ℃/26.6Pa of 121g, 4-cyclohexane dicarboxylic acid diallyl (yield: 95%).Obtain like this 1,4-cyclohexane dicarboxylic acid diallyl is called " sample A ".
Embodiment 2
Be reflected under the condition identical with embodiment 1 and cause, different is the calcium oxide of the calcium hydroxide of 0.25g being changed into 0.25g.Reaction times and the yield of analyzing with GC are illustrated in the table 1.
Embodiment 3
Be reflected under the condition identical with embodiment 1 and cause, different is the magnesium hydroxide of the calcium hydroxide of 0.25g being changed into 0.25g.Reaction times and the yield of analyzing with GC are illustrated in the table 1.
Be reflected under the condition identical with embodiment 1 and cause, different is the hydrated barta of the calcium hydroxide of 0.25g being changed into 0.25g.Reaction times and the yield of analyzing with GC are illustrated in the table 1.
Table 1
| Reaction times | Yield (based on CHDM) with the GC analysis | |
| Embodiment 1 | 10 hours | 98.8％ |
| Embodiment 2 | 20 hours | 93.2％ |
| Embodiment 3 | 34 hours | 67.9 |
| Embodiment | ||
| 4 | 20 hours | 91.4％ |
Be reflected under the condition identical with embodiment 1 and cause, different is the sodium acetate of the potassium acetate of 0.05g being changed into 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 2.
Be reflected under the condition identical with embodiment 1 and cause, different is the Tripotassium phosphate of the potassium acetate of 0.05g being changed into 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 2.
Be reflected under the condition identical with embodiment 1 and cause, different is the sodium bicarbonate of the potassium acetate of 0.05g being changed into 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 2.
Be reflected under the condition identical with embodiment 1 and cause, different is the vitriolate of tartar of the potassium acetate of 0.05g being changed into 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 2.
Be reflected under the condition identical with embodiment 1 and cause, different is the Repone K of the potassium acetate of 0.05g being changed into 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 2.
Be reflected under the condition identical with embodiment 1 and cause, different is the salt of wormwood of the potassium acetate of 0.05g being changed into 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 2.
Embodiment 11
Be reflected under the condition identical with embodiment 1 and cause, different is the Quilonum Retard of the potassium acetate of 0.05g being changed into 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 2.
Embodiment 12
Be reflected under the condition identical with embodiment 1 and cause, different is the yellow soda ash of the potassium acetate of 0.05g being changed into 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 2.
Embodiment 13
Be reflected under the condition identical with embodiment 1 and cause, different is the rubidium carbonate of the potassium acetate of 0.05g being changed into 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 2.
Table 2
| Catalyzer | Reaction times | Yield (based on CHDM) with the |
| Embodiment | ||
| 5 | 14 hours | 93.6 |
| Embodiment | ||
| 6 | 11 hours | 94.6 |
| Embodiment | ||
| 7 | 13 hours | 91.9 |
| Embodiment | ||
| 8 | 16 hours | 95.1 |
| Embodiment | ||
| 9 | 17 hours | 94.7 |
| Embodiment | ||
| 10 | 16 hours | 97.2％ |
| Embodiment 11 | 38 hours | 91.3％ |
| Embodiment 12 | 25 hours | 94.9％ |
| Embodiment 13 | 15 hours | 96.8％ |
Embodiment 14
To the CHDM of the 300ml three-necked flask interpolation 100g with thermometer and rectifying tower, the methallyl alcohol of 149g, the calcium hydroxide of 0.25g and 0.05g potassium acetate, and reaction under the oil bath that transfers to 120 ℃ is heated.Reaction was carried out 15 hours, distilled out with reaction from rectifying tower simultaneously and carried out and the methyl alcohol that produces.After reaction is finished, analyze to confirm by GC, obtained 94.0% 1,4-cyclohexane dicarboxylic acid dimethyl allyl ester is based on CHDM.
Embodiment 15
Initiation reaction under the condition identical with embodiment 1 only is to use 1 of 100g, and 3-cyclohexane dicarboxylic acid dimethyl ester replaces the CHDM of 100g.Reaction times and the yield of analyzing with GC are illustrated in the table 3.
Embodiment 16
Initiation reaction under the sundries identical with embodiment 1 only is to use 1 of 100g, and 2-cyclohexane dicarboxylic acid dimethyl ester replaces the CHDM of 100g.Reaction times and the yield of analyzing with GC are illustrated in the table 3.
Embodiment 17
Initiation reaction under the condition identical with embodiment 1 only is to use 1,2 of 129g, and 4-hexanaphthene tricarboxylic acid trimethyl replaces the CHDM of 100g.Reaction times and the yield of analyzing with GC are illustrated in the table 3.
Embodiment 18
Initiation reaction under the condition identical with embodiment 1 only is to use 1,2,4 of 158g, and 5-hexanaphthene tetracarboxylic acid tetramethyl ester replaces the CHDM of 100g and the consumption of vinyl carbinol is changed into 240g from 120g.Reaction times and the yield of analyzing with GC are illustrated in the table 3.
Embodiment 19
Initiation reaction under the condition identical with embodiment 1 only is to use 1 of 114g, and 4-cyclohexane dicarboxylic acid diethyl ester replaces the CHDM of 100g.Reaction times and the yield of analyzing with GC are illustrated in the table 3.
Embodiment 20
Initiation reaction under the condition identical with embodiment 1 only is to use 1 of 128g, and 4-cyclohexane dicarboxylic acid diisopropyl ester replaces the CHDM of 100g.Reaction times and the yield of analyzing with GC are illustrated in the table 3.
Table 3
| Reaction times | Yield (based on raw material) with GC or LC analysis | |
| Embodiment 14 | 15 hours | 94.0％(GC) |
| Embodiment 15 | 10 hours | 97.1％(GC) |
| Embodiment 16 | 20 hours | 91.1％(GC) |
| Embodiment 17 | 30 hours | 92.9％(LC) |
| Embodiment 18 | 20 hours | 87.1％(LC) |
| Embodiment 19 | 15 hours | 96.9％(GC) |
| Embodiment 20 | 25 hours | 93.4％(GC) |
Embodiment 21
Initiation reaction under the condition identical with embodiment 1 only is to use the calcium hydroxide of 2.0g to replace the calcium hydroxide of 0.25g and the potassium acetate of 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 4.
Embodiment 22
Initiation reaction under the condition identical with embodiment 1 only is to use the salt of wormwood of 1.0g to replace the calcium hydroxide of 0.25g and the potassium acetate of 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 4.
Embodiment 23
Initiation reaction under the condition identical with embodiment 1 only is to use the metatitanic acid tetra isopropyl ester of 2.0g to replace the calcium hydroxide of 0.25g and the potassium acetate of 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 4.
Embodiment 24
Initiation reaction under the condition identical with embodiment 1 only is to use the sodium methylate of 2.0g to replace the calcium hydroxide of 0.25g and the potassium acetate of 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 4.
Embodiment 25
Initiation reaction under the condition identical with embodiment 1, only be to use the calcium hydroxide of 2.0g to replace the calcium hydroxide of 0.25g and the potassium acetate of 0.05g, use the dibutyltin oxide of 2.0g, pressure is changed into 0.6Mpa (gauge pressure) and oil bath temperature is changed into 170 ℃ from 120 ℃ from normal atmosphere.Reaction times and the yield of analyzing with GC are illustrated in the table 4.
Embodiment 26
Initiation reaction under the condition identical with embodiment 1 only is to use the Acetyl Acetone acid zinc of 2.0g to replace the calcium hydroxide of 0.25g and the potassium acetate of 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 4.
Embodiment 27
Initiation reaction under the condition identical with embodiment 1 only is to use the Acetyl Acetone acid hafnium of 2.0g to replace the calcium hydroxide of 0.25g and the potassium acetate of 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 4.
Embodiment 28
Initiation reaction under the condition identical with embodiment 1 only is to use 1 of 2.0g, and 4-diazabicyclo [2.2.2] octane replaces the calcium hydroxide of 0.25g and the potassium acetate of 0.05g.Reaction times and the yield of analyzing with GC are illustrated in the table 4.
Table 4
| Reaction times | Yield (based on DMI) with the GC analysis | Note | |
| Embodiment 21 | 18 hours | 95.8％ | Not painted |
| Embodiment 22 | 12 hours | 96.2％ | Painted |
| Embodiment 23 | 20 hours | 94.7％ | Light colored |
| Embodiment 24 | 18 hours | 55.7％ | Painted |
| Embodiment 25 | 25 hours | 95.9％ | Not painted |
| Embodiment 26 | 30 hours | 40.7％ | Light colored |
| Embodiment 27 | 25 hours | 90.5％ | Light colored |
| Embodiment 28 | 15 hours | 95.0％ | Light colored |
The comparative example 1
In the reactor assembly identical, add 1 of 100g with embodiment 1, the 4-cyclohexane dicarboxylic acid, the vinyl carbinol of 120g, the benzene of 100g and the sulfuric acid of 1g are transferring to reaction under 120 ℃ the oil bath heating again.When separating out 23g water, termination reaction by GC analytical reaction product, finds that it contains 5% diallyl ether (based on 1,4-cyclohexane dicarboxylic acid diallyl).Solution is transferred in the 1L separatory funnel, the 50g1% aqueous sodium hydroxide solution is joined wherein, carry out the liquid separation operation, remove water again.Repeat identical operations once more, under reduced pressure distill out benzene and vinyl carbinol in the oil phase then by vaporizer.After this, the not directly distillation under reduced pressure of component that distills out by vaporizer, acquisition is the 177.7g 1 of light yellow transparent liquid, 4-cyclohexane dicarboxylic acid diallyl (yield: 94%).The sulphur content of this liquid is analyzed by chloro-sulphur analyser TSX-10 type (being produced by Mitsubishi Kagaku), is defined as 30 quality ppm.This 1,4-cyclohexane dicarboxylic acid diallyl is called " sample B ".
The stability in storage evaluation of sample A and sample B
Be determined at after producing soon sample A and B and after producing 25 ℃ of the sample A in 1 year of storage and Hazen colours of B down.The result provides in following table 5.
Table 5
Embodiment 29 (production of alicyclic allyl ester compound)
The sample A that in the 1L three-necked flask that has water distilling apparatus, adds 120.0g, the propylene glycol of 24.1g and the dibutyltin oxide of 0.12g.Under nitrogen gas stream, this system is heated to 180 ℃, and distills the vinyl carbinol that is produced.When distilling about 27.7g vinyl carbinol, the reactive system pressure inside is reduced to 1.33kPa, thereby has increased the distillation rate of vinyl carbinol.After distilling out the vinyl carbinol of theoretical amount, reactive system was heated other 1 hour, under 180 ℃ and 0.13kPa, kept 1 hour then.After this, cooling reactor then, has obtained the allyl ester compound (hereinafter being referred to as " sample C ") of 107.5g.
The sample C of Huo Deing is by gc analysis (GC-14B like this, produce by Shimadzu Corp., under 160 ℃ steady temperature condition, use the pillar OV-17 of hydrogen flame ionization detector and 0.5m), found that and contain 1 of 13 quality %, 4-cyclohexane dicarboxylic acid diallyl.
Fig. 1 has shown the 400MHz of this sample
1The H-NMR wave spectrogram.
Comparative example 2 (production of alicyclic allyl ester compound)
The sample B that in the 1L three-necked flask that has water distilling apparatus, adds 120.0g, the propylene glycol of 24.1g and the dibutyltin oxide of 0.12g.Under nitrogen gas stream, this system is heated to 180 ℃, and distills the vinyl carbinol that is produced.When distilling about 27.7g vinyl carbinol, the reactive system pressure inside is reduced to 1.33kPa, thereby has increased the distillation rate of vinyl carbinol.After distilling out the vinyl carbinol of theoretical amount, reactive system was heated other 1 hour, under 180 ℃ and 0.13kPa, kept 1 hour again.After this, cooling reactor then, has obtained the allyl ester compound (hereinafter being referred to as " sample D ") of 107.5g.
The sample D of Huo Deing is by gc analysis (GC-14B like this, produce by Shimadzu Corp., under 160 ℃ steady temperature condition, use the pillar OV-17 of hydrogen flame ionization detector and 0.5m), found that and contain 1 of 12 quality %, 4-cyclohexane dicarboxylic acid diallyl.
Fig. 2 has shown the 400MHz of this sample
1The H-NMR wave spectrogram.
Embodiment 30 (mensuration of the refractive index of lens, Abb and Barcol hardness, and the evaluation of dyeing speck)
As shown in table 6, with 95.0 mass parts glycol ethers two (allyl carbonate) (CR-39, trade(brand)name are produced by PPG), 5 mass parts sample C and 3 mass parts di-isopropyl peroxydicarbonate (IPP) blend under agitation and mixing form liquid composite fully uniformly.Measure the viscosity of this moment.After this, the container that will contain this solution is put into the moisture eliminator that can reduce pressure, and reduces pressure about 15 minutes with vacuum pump, so that remove gas in the solution again.The gained liquid composite injects the mould of being made by glass mould that is used for the ophthalmology plastic lens and resin system liner by syringe, notice simultaneously preventing that the interior of gas from mixing, heated 7 hours down at 40 ℃ according to making then, heated 10 hours down at 40-60 ℃, heating is 3 hours under 60-80 ℃, heats 1 hour down and solidifies in baking oven 85 ℃ of temperature program(me)s that heated 2 hours down at 80 ℃.
Measure the refractive index of the lens that obtain like this, Abb and Barcol hardness revalue uneven dyeing.Their result provides in table 6.
Table 6
Comparative example 3 and 4
Prepare composition according to the mode identical, measure viscosity, measure refractive index, Abb and the Barcol hardness of lens then, revalue uneven dyeing with blend shown in the table 6 with embodiment 1.The result provides in table 6.
Industrial applicability
According to the present invention, use has Arrcostab (never using as the initiation material of (methyl) allyl ester of the polyacid with alicyclic structure in the past) and (methyl) allyl alcohol of the polyacid of alicyclic structure, in the presence of ester exchange catalyst, react, produced corresponding alicyclic (methyl) allyl ester monomer, thereby can provide industrial process with low cost, can not produce any accessory substance such as diallyl ether, and this product can have excellent extended storage stability. The present invention's alicyclic (methyl) allyl ester compound that is formed by alicyclic (methyl) the allyl ester monomer that obtains by said method and polyalcohol by can provide with poly-(allyl carbonate) resin-bonded use have excellence can chromatic plastic lens.
Claims (2)
1. produce alicyclic (methyl) allyl ester monomer methods, be included in the multivalence alkyl ester and vinyl carbinol and/or the methallyl alcohol reaction that make polyprotonic acid under the existence of transesterification catalyst with alicyclic structure.
2. the desired method of claim 1, wherein transesterification catalyst is to be selected from an alkali metal salt of organic acid and/or mineral acid and the oxyhydroxide and/or the hopcalite of alkaline-earth metal, the organometallic complex of Hf, Mn, U, Zn, Cd, Zr, Pb, Ti, Co and Sn, organo-tin compound, organic titanic compound, tertiary amine, an alkali metal salt of carbonic acid and/or alkaline earth salt, and at least a in the alkali-metal alkyl alcoholate.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP181489/00 | 2000-06-16 | ||
| JP2000181489 | 2000-06-16 | ||
| JP181489/2000 | 2000-06-16 | ||
| US22120900P | 2000-07-27 | 2000-07-27 | |
| US60/221,209 | 2000-07-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2008100984772A Division CN101279913B (en) | 2000-06-16 | 2001-06-14 | Process for producing alicyclic (meth) allyl esters for plastic lens compositions |
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| CN1436162A CN1436162A (en) | 2003-08-13 |
| CN100406426C true CN100406426C (en) | 2008-07-30 |
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| CN2008100984772A Expired - Fee Related CN101279913B (en) | 2000-06-16 | 2001-06-14 | Process for producing alicyclic (meth) allyl esters for plastic lens compositions |
| CNB018110983A Expired - Fee Related CN100406426C (en) | 2000-06-16 | 2001-06-14 | Process for production of alicyclic (meth) allyl esters for plastic lens compositions |
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| CN2008100984772A Expired - Fee Related CN101279913B (en) | 2000-06-16 | 2001-06-14 | Process for producing alicyclic (meth) allyl esters for plastic lens compositions |
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| Country | Link |
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| US (2) | US6545120B1 (en) |
| EP (1) | EP1289924B1 (en) |
| KR (1) | KR100549875B1 (en) |
| CN (2) | CN101279913B (en) |
| AT (1) | ATE324363T1 (en) |
| AU (1) | AU2001264285A1 (en) |
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| WO2002079140A1 (en) * | 2001-03-26 | 2002-10-10 | Showa Denko K. K. | Novel polyvalent carboxylic acid esters and their use in plastic lens compositions |
| US6803341B2 (en) * | 2002-01-18 | 2004-10-12 | Chinese Petroleum Corporation | Method of a high stability selectable hydrogenate catalyst producing and using for DMCHD manufacturing |
| TWI490312B (en) * | 2006-04-06 | 2015-07-01 | Showa Denko Kk | Transparent conductive substrate |
| CN101328124B (en) * | 2008-08-01 | 2011-01-12 | 河北工业大学 | Ester exchange method for synthesizing ethylene diglycol diene propyl carbonic ether |
| KR101099127B1 (en) * | 2008-10-16 | 2011-12-26 | 한화케미칼 주식회사 | Method of preparing of 60% or more cis-di(C4-C20)alkyl cyclohexane-1,4-dicarboxylate |
| US9145371B2 (en) * | 2013-06-11 | 2015-09-29 | Rhoda Operations | Process for the preparation of (meth)acrylic esters and derivatives |
| EP3133058B1 (en) | 2014-04-16 | 2019-05-29 | Toagosei Co., Ltd. | Multifunctional (meth)acrylate manufacturing method |
| WO2016104389A1 (en) | 2014-12-22 | 2016-06-30 | 昭和電工株式会社 | Active energy ray-curable composition, and use thereof |
| CN108350106B (en) * | 2015-11-27 | 2021-05-14 | 三井化学株式会社 | Polymerizable composition for optical material, optical material obtained from the composition, and plastic lens |
| CN108699314B (en) * | 2016-03-31 | 2021-07-06 | 株式会社大阪曹达 | Photocurable resin composition, ink, and coating material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0593877A1 (en) * | 1992-08-26 | 1994-04-27 | Showa Denko Kabushiki Kaisha | Composition for optical material |
| WO1999017137A1 (en) * | 1997-09-30 | 1999-04-08 | Akzo Nobel N.V. | Ophthalmic lenses |
| WO1999038899A1 (en) * | 1998-01-30 | 1999-08-05 | Ppg Industries Ohio, Inc. | Polymerizable polyol(allyl carbonate) composition |
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| JPH07103195B2 (en) * | 1987-10-14 | 1995-11-08 | 株式会社日立製作所 | Optical material |
| US5694195A (en) * | 1994-09-30 | 1997-12-02 | Signet Armorlite, Inc. | Polyester resin-based high index ophthalmic lenses having improved optical uniformity and/or tintability |
| NZ303624A (en) * | 1995-03-08 | 1999-01-28 | Du Pont | Reactive organosilicons as coatings, adhesives, and sealants |
| CN1214256C (en) * | 2000-04-11 | 2005-08-10 | 昭和电工株式会社 | Plastic lens material production process of the material, composition for plastic lens, plastic lens obtained by curing the composition, and production process of the plastic lens |
| AU2001264230A1 (en) * | 2000-06-16 | 2001-12-24 | Showa Denko K K | Material for plastic lens, production process of the material, composition for plastic lens, plastic lens obtained by curing the composition, and production process of the plastic lens |
| EP1328560A2 (en) * | 2000-09-28 | 2003-07-23 | Showa Denko K.K. | Plastic lens composition, plastic lens, and process for producing the plastic lens |
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2001
- 2001-06-14 EP EP01938672A patent/EP1289924B1/en not_active Expired - Lifetime
- 2001-06-14 WO PCT/JP2001/005081 patent/WO2001096274A1/en active IP Right Grant
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0593877A1 (en) * | 1992-08-26 | 1994-04-27 | Showa Denko Kabushiki Kaisha | Composition for optical material |
| WO1999017137A1 (en) * | 1997-09-30 | 1999-04-08 | Akzo Nobel N.V. | Ophthalmic lenses |
| WO1999038899A1 (en) * | 1998-01-30 | 1999-08-05 | Ppg Industries Ohio, Inc. | Polymerizable polyol(allyl carbonate) composition |
Also Published As
| Publication number | Publication date |
|---|---|
| US6545120B1 (en) | 2003-04-08 |
| ATE324363T1 (en) | 2006-05-15 |
| US20030144460A1 (en) | 2003-07-31 |
| WO2001096274A1 (en) | 2001-12-20 |
| US20030055203A1 (en) | 2003-03-20 |
| CN101279913B (en) | 2012-01-11 |
| EP1289924B1 (en) | 2006-04-26 |
| EP1289924A1 (en) | 2003-03-12 |
| DE60119099D1 (en) | 2006-06-01 |
| US6739720B2 (en) | 2004-05-25 |
| CN101279913A (en) | 2008-10-08 |
| AU2001264285A1 (en) | 2001-12-24 |
| KR100549875B1 (en) | 2006-02-08 |
| CN1436162A (en) | 2003-08-13 |
| KR20030009527A (en) | 2003-01-29 |
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